A Comparative Study on Analysis of Ginsenosides in American Ginseng Root Residue by HPLC-DAD-ESI-MS and UPLC-HRMS-MS/MS

Ginseng (Panax quinquefolius), a popular herbal and nutritional supplement consumed worldwide, has been demonstrated to possess vital biological activities, which can be attributed to the presence of ginsenosides. However, the presence of ginsenosides in ginseng root residue, a by-product obtained during processing of ginseng beverage, remains unexplored. The objectives of this study were to develop a high-performance liquid chromatography-photodiode array detection-mass spectrometry (HPLC-DAD-ESI-MS) and an ultra-high-performance-liquid-chromatography-tandem mass spectrometry (UPLC-HRMS-MS/MS) method for the comparison of ginsenoside analysis in ginseng root residue. Results showed that by employing a Supelco Ascentis Express C18 column (150 × 4.6 mm ID, particle size 2.7 μm) and a gradient mobile phase of deionized water and acetonitrile with a flow rate at 1 mL/min and detection at 205 nm, a total of 10 ginsenosides, including internal standard saikosaponin A, were separated within 18 min and detected by HPLC-DAD-ESI-MS. Whereas with UPLC-HRMS-MS/MS, all the 10 ginsenosides were separated within six minutes by using an Acquity UPLC BEH C18 column (50 × 2.1 mm ID, particle size 1.7 μm, 130 Å) and a gradient mobile phase of ammonium acetate and acetonitrile with column temperature at 50 °C, flow rate at 0.4 mL/min and detection by selected reaction monitoring (SRM) mode. High accuracy and precision was shown, with limit of quantitation (LOQ) ranging from 0.2–1.9 μg/g for HPLC-DAD-ESI-MS and 0.269–6.640 ng/g for UPLC-HRMS-MS/MS. The contents of nine ginsenosides in the ginseng root residue ranged from <LOQ-26.39 mg/g by HPLC-DAD-ESI-MS and <LOQ-21.25 mg/g by UPLC-HRMS-MS/MS, with a total amount of 38.37 and 34.71 mg/g, respectively.     

Dielectric response of thin water films: a thermodynamic perspective

The surface of a polar liquid presents a special environment for the solvation and organization of charged solutes, which differ from bulk behaviors in important ways. These differences have motivated many attempts to understand electrostatic response at aqueous interfaces in terms of a spatially varying dielectric permittivity, typically concluding that the dielectric constant of interfacial water is significantly lower than in the bulk liquid. Such analyses, however, are complicated by the potentially nonlocal nature of dielectric response over the short length scales of interfacial heterogeneity. Here we circumvent this problem for thin water films by adopting a thermodynamic approach. Using molecular simulations, we calculate the solvent''s contribution to the reversible work of charging a parallel plate capacitor. We find good agreement with a simple dielectric continuum model that assumes bulk dielectric permittivity all the way up to the liquid''s boundary, even for very thin (∼1 nm) films. This comparison requires careful attention to the placement of dielectric boundaries between liquid and vapor, which also resolves apparent discrepancies with dielectric imaging experiments.

Free energy calculations from molecular simulations reveal that water''s interfacial dielectric response is well-described by bulk properties.     

Proton Transfer of Phenanthridone in the Lowest Excited Singlet State in Moderately Concentrated Mineral Acid Solutions

A modified form of the steady state treatment for the determination of excited state proton transfer rate constants was successfully applied to a variety of oxygen and nitrogen center aromatic excited acids. These compounds shared the characteristic of being more acidic in the lowest excited singlet state (S₁) than in the ground electronic state (S₀) and of requiring a concentrated mineral acid medium for protonation. This treatment was extended to phenanthridone, the lactam of 6-hydroxyphenanthridine, which is a weak enough base in the ground and the excited states to require moderately concentrated mineral acids for protonation, and becomes a stronger base in the excited state than it is in the ground state. Phenanthridone exists as an -lactam and is a weaker base in the ground and excited states than the -lactams derived from 2-hydroxypyridine, 2-hydroxyquinoline, and 1-hydroxyisoquinoline. It is also a much weaker base than the vinylogous -lactams. The reasons for this are discussed here.     

The Conformation of Sterically Congested Seven-Membered Rings Containing Tetracoordinate Germanium(IV): A First X-Ray Crystallographic Structure Determination

The X-ray crystallographic analysis of 6,6-dimethyl-2,4,8,10-tetra-tert-octyl-dibenzo[d,f][1,3,2]dioxagermepin, 1 is reported. In the solid-state conformation of 1, the dihedral angle about the C─C sp²-sp ² σ bond connecting the two aryl rings is 50.1°. The observed C₂ symmetry in the solid-state conformation of 1 is consistent with the previously suggested solution conformation.     

The Geometry of Barotropic Flow

In this paper we construct a new noninvariant Riemannian metric on the semidirect product of the diffeomorphism group of a manifold and the space of positive functions on that manifold, which has the property that certain geodesics give the equations of barotropic fluid mechanics. We compute a formula for its curvature, analyze the sign of the curvature, and determine directly the growth of Jacobi fields in a few special cases.     

Spectroscopic fingerprints of valence and spin states in manganese oxides and fluorides

We performed a systematic study of soft X-ray absorption spectroscopy in various manganese oxides and fluorides. Both Mn L-edges and ligand (O and F) K-edges are presented and compared with each other. Despite the distinct crystal structure and covalent/ionic nature in different systems, the Mn-L spectra fingerprint the Mn valence and spin states through spectral lineshape and energy position consistently and evidently. The clear O- and F-K pre-edge features in our high resolution spectra enable a quantitative definition of the molecular orbital diagram with different Mn valence. In addition, while the binding energy difference of the O-1s core electrons leads to a small shift of the O-K leading edges between trivalent and quadrivalent manganese oxides, a significant edge shift, with an order of magnitude larger in energy, was found between divalent and trivalent compounds, which is attributed to the spin exchange stabilization of half-filled 3d system. This shift is much enhanced in the ionic fluoride system. This work provides the spectroscopic foundation for further studies of complicated Mn compounds.     

APPLICATIONS OF MULTICOMPONENT ASSEMBLY PROCESSES TO THE FACILE SYNTHESES OF DIVERSELY FUNCTIONALIZED NITROGEN HETEROCYCLES

Several multicomponent assembly processes have been developed for the synthesis of intermediates that may be elaborated by a variety of cyclizations to generate a diverse array of highly functionalized heterocycles from readily-available starting materials. The overall approach enables the efficient preparation of libraries of small molecules derived from fused, privileged scaffolds.